Biomass-based emulsion and application thereof in waterproof treatment of paper surface

Abstract

The invention relates to a biomass-based emulsion and application thereof in waterproof treatment of paper surfaces. The biomass-based emulsion provided by the invention comprises a biomass-based material and biological wax, the biomass-based material comprises a micron-sized structure and a nano-sized structure distributed on the micron-sized structure. The use amount of the biological wax can be reduced by coating the emulsion on the surface of paper, and the obtained biological wax layer is small in thickness and easier to recover; and the emulsion coating process can be directly added to the existing papermaking process, so that the papermaking production process is simplified.

Description

Technical Field

[0001] This invention belongs to the field of papermaking technology and relates to a biomass-based emulsion and its application in waterproofing paper surfaces. Background Technology

[0002] The widespread use of single-use non-degradable plastic products has led to serious environmental pollution problems, especially microplastic pollution. Currently, some countries have completely banned plastics in the single-use sector and have begun levying plastic taxes; my country is also gradually beginning to ban plastics. Therefore, against the backdrop of a global ban on plastics, there is an urgent need to find biodegradable alternatives to single-use products.

[0003] Replacing plastic with paper is currently the global solution for disposable products (such as packaging, paper cups, paper straws, paper plates, and even paper bottles for takeout). However, a core problem exists: traditional paper products have poor water and oil resistance, making them difficult to heat-seal and bond. The first-generation solution involved coating the paper surface, but because the coating material was still a non-degradable traditional polymer, such as PP or PE, and coating involved melting and applying the polymer, the resulting thick coating still caused more severe microplastic pollution and made paper recycling and pulping difficult. The second-generation solution used polylactic acid (PLA) instead of PE or PP for coating the paper surface, but the following problems remained: 1) PLA cannot degrade naturally and can only be composted, making it unpopular in Europe and the United States for disposable products; 2) The thick PLA layer obtained during coating resulted in a high PLA basis weight per unit area and high cost, while also presenting challenges for recycling and pulping. Currently, using emulsion coating technology instead of coating technology reduces both the process difficulty and the amount of barrier material used, thus lowering overall costs and becoming a trend in paper product development. However, there is still a lack of mature solutions that are entirely biomass or entirely natural and fully biodegradable. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a biomass-based emulsion and its application in paper waterproofing treatment.

[0005] The technical solution provided by this invention is as follows:

[0006] A biomass-based emulsion, the biomass-based emulsion comprising a biomass-based material and a biowax, wherein the biomass-based material comprises a micron-scale structure and a nano-scale structure distributed on the micron-scale structure.

[0007] The present invention also provides a biomass-based emulsion, the biomass-based emulsion comprising a biomass-based dispersion and a biowax, the biomass-based dispersion comprising the above-mentioned biomass-based material and dispersing agent, the biomass-based material and the biowax being distributed in the dispersing agent, the dispersing agent being a solvent system capable of continuously dispersing the biomass-based material and the biowax.

[0008] The present invention also provides a biomass-based emulsion, the biomass-based emulsion comprising biowax and surface-modified biomass-based material or surface-modified biomass-based dispersion; the surface-modified biomass-based dispersion comprising surface-modified biomass-based material and dispersing agent, wherein the surface-modified biomass-based material and biowax are dispersed in the dispersing agent; the dispersing agent is a solvent system capable of continuously dispersing the surface-modified biomass-based material and biowax; the surface-modified biomass-based material is a surface-modified version of the above-mentioned biomass-based material; or a material prepared by the preparation method of the biomass-based material, except that the raw biomass is replaced with surface-modified biomass.

[0009] This invention also provides a biomass-based emulsion, comprising biowax and a substituted biomass-based material or a substituted biomass-based dispersion; the substituted biomass dispersion comprises a substituted biomass-based material and a dispersing agent, wherein the substituted biomass-based material and the biowax are dispersed in the dispersing agent; the dispersing agent is a solvent system capable of continuously dispersing the substituted biomass-based material and the biowax; the biomass-based material in the substituted biomass-based dispersion is the aforementioned biomass-based material; or a material prepared by the method for preparing the biomass-based material, except that the raw biomass is replaced with surface-modified biomass.

[0010] This invention also provides a biomass-based emulsion, comprising a multi-component biomass-based dispersion and biowax, wherein the continuous phase of the biomass-based emulsion is a dispersing agent, and the dispersed phase of the biomass-based emulsion contains biowax and functional components, and further contains at least one of the following components 1) to 3):

[0011] 1) The above-mentioned biomass-based materials;

[0012] 2) The above-mentioned alternative biomass-based materials;

[0013] 3) The above-mentioned surface-modified biomass-based materials.

[0014] The present invention also provides the application of the above-mentioned biomass-based emulsion in paper waterproofing treatment.

[0015] The beneficial effects of this invention are:

[0016] The biomass-based emulsion prepared by this invention includes biomass-based materials and bio-waxes (such as beeswax, palm wax, etc.). Among them, the biomass-based materials have excellent Pickering emulsification effect, which can stabilize organic components such as bio-waxes and form a fully biomass-based emulsion with high stability of bio-wax particles in the aqueous phase. When the biomass-based emulsion of this invention is used for paper waterproofing treatment, high-barrier paper plastic substitute products can be prepared.

[0017] The biomass-based emulsion prepared by this invention uses fully biodegradable materials and can be directly degraded naturally.

[0018] The emulsion of this invention exhibits high stability and homogeneity. The biomass-based emulsion maintains high stability even after being stored at room temperature for more than 3 months, and is minimally affected by dispersing agents (such as water hardness and electrolytes). The biomass-based emulsion of this invention is highly formable; the biomass-based materials, surface-modified biomass-based materials, and substituted biomass-based materials are easily compatible with various biowaxes and additives, synergistically forming high-performance products.

[0019] By coating the emulsion of the present invention onto the surface of paper, the amount of biowax used can be reduced, and the resulting biowax layer is thinner and easier to recycle; moreover, the emulsion coating process can be directly added to the existing papermaking process and simplify the papermaking production process. Attached Figure Description

[0020] Figure 1 Digital photographs of the micro / nano cellulose dispersion obtained in Example 1, from left to right, show the state of the dispersion after standing for 0, 1, 10, 30, and 100 days.

[0021] Figure 2 Microscopic images of the micro / nano cellulose dispersion prepared in Example 1 (scale bar: 100 μm).

[0022] Figure 3 Microscopic image of the dried micro-nano dispersion of Example 2 (scale bar: 100 μm).

[0023] Figure 4 The particle size distribution curve of the dispersion obtained in Example 1 was tested using a laser particle size analyzer.

[0024] Figure 5 SEM image of the flocculent biomass-based material prepared in Example 8.1;

[0025] Figure 6 SEM image of the tentacle-like biomass-based material prepared in Example 8.9;

[0026] Figure 7 SEM image of the feather-like biomass-based material prepared in Example 8.12;

[0027] Figure 8 SEM image of the broom-shaped biomass-based material prepared in Example 8.17;

[0028] Figure 9 SEM image of the sheet-like biomass-based material prepared in Example 8.28;

[0029] Figure 10 SEM image of the sponge-like biomass-based material prepared in Example 8.31;

[0030] Figure 11 SEM image of the dendritic biomass-based material prepared in Example 8.33;

[0031] Figure 12 SEM image of the fibrous biomass-based material prepared in Example 9.39.

[0032] Figure 13 These are optical photographs of the emulsions of Example 1 and Comparative Example 1.

[0033] Figure 14 This is a diagram illustrating the high barrier effect of the emulsion-coated paper using the present invention. Detailed Implementation

[0034] [Preparation methods for biomass-based materials]

[0035] This invention provides a method for preparing biomass-based materials, wherein the preparation method is selected from method A or method B, wherein method A includes the following steps:

[0036] Biomass is dissolved in a solvent to form a biomass solution;

[0037] The above-mentioned biomass solution and coagulation bath are added to a crushing device, and mechanical crushing is performed while they are being mixed; the biomass-based material is thus prepared.

[0038] Method B includes the following steps: pouring a biomass solution into a coagulation bath to form a biomass gel; and performing micro-nano processing on the biomass gel through mechanical crushing to obtain the biomass-based material.

[0039] The biomass-based material includes a micron-scale structure and a nano-scale structure distributed on the micron-scale structure.

[0040] The mechanical crushing process includes methods such as homogenizers, colloid mills, or ball mills.

[0041] According to an embodiment of the present invention, in method A, after the biomass solution and coagulation bath are crushed, the biomass-based material is obtained by filtration and washing.

[0042] According to an embodiment of the present invention, in method A, after the washing step, a concentration step can be flexibly selected according to the application or field.

[0043] According to an embodiment of the present invention, method B further includes a washing step before mechanical crushing.

[0044] According to embodiments of the present invention, the reagents used in the washing steps of methods A and B are selected from at least one of water, alcohol, an alcohol-water mixture, an aqueous HCl solution, an aqueous NaOH solution, and an aqueous inorganic salt solution, preferably water and / or alcohol, such as water. The alcohol is, for example, at least one of methanol, ethanol, ethylene glycol, propanol, glycerol, isopropanol, n-butanol, and isobutanol, preferably methanol, ethanol, or ethylene glycol, with ethanol being an example. Further, the ratio of alcohol to water in the alcohol-water mixture is not particularly limited, for example, it can be (1-10):(1-10), preferably 1:(1-10), with examples of 1:2, 1:3, 1:4, 1:5, and 1:10. Exemplarily, the inorganic salt can be selected from at least one of Na₂SO₄, NaCl, KCl, CaCl₂, MgCl₂, FeCl₃, KNO₃, and NaNO₃. The reagents used may be the same as or different from the coagulation bath.

[0045] In method A of the present invention, biomass is first completely or partially dissolved in a solvent, and the ordered structure of natural macromolecules (taking cellulose as an example, including lignin, hemicellulose, cellulose, etc.) in the biomass is completely or partially destroyed by dissolution or swelling to form a biomass solution; the biomass solution is mixed with a coagulation bath and simultaneously subjected to crushing treatment: the biomass solution comes into contact with the coagulation bath and rapidly undergoes a gelation transformation to form a loose gel network structure. At the same time, the loose gel network structure is instantly crushed under the crushing treatment of the crushing device, thereby obtaining the biomass-based material of the present invention.

[0046] The inventors unexpectedly discovered that in method A, if the two-phase fluids of biomass solution and coagulation bath are simultaneously injected into the crushing device, the mixture will be crushed. By maximally compressing the gelation time, the strength of the biomass gel is reduced, thereby effectively reducing the crushing difficulty and mechanical energy consumption. A large amount of biomass material can be prepared in a short time with high production efficiency.

[0047] According to an embodiment of the present invention, in method A or method B, the biomass solution may be a homogeneous solution in which the biomass is completely dissolved or a heterogeneous solution in which the biomass is partially dissolved.

[0048] According to an embodiment of the present invention, in method A or method B, the biomass-based material formed by the homogeneous solution is type II cellulose, and the biomass-based material formed by the heterogeneous solution is a complex of type I cellulose and type II cellulose.

[0049] According to an embodiment of the present invention, in method A or method B, there is no particular limitation on the mass percentage concentration of biomass in the biomass solution, for example, the mass percentage concentration of biomass in the biomass solution is ≥2%, preferably ≥3%. Further research has found that, using the method of the present invention, even if the mass percentage concentration of biomass in the biomass solution is ≥4%, high-efficiency and low-energy-consumption production can still be carried out.

[0050] According to an embodiment of the present invention, in method A or method B, in order to improve production efficiency, the mass percentage concentration of biomass in the biomass solution is greater than or equal to 4%, preferably greater than or equal to 6%, and more preferably greater than or equal to 8%.

[0051] According to an embodiment of the present invention, in method A or method B, the mass percentage concentration of biomass in the biomass solution can reach 8%, preferably 10%, and more preferably 20%, for example 5%, 8%, 10%, 12%, 15%, 18%, 25%, or 30%.

[0052] As an example, when the biomass raw material is wood pulp, the mass percentage concentration of biomass in the corresponding biomass solution can reach 10%; when the biomass raw material is straw, the mass percentage concentration of biomass in the corresponding biomass solution can reach 30%.

[0053] According to an embodiment of the present invention, the volume ratio of the biomass solution to the coagulation bath is 1:1 to 1:200, preferably 1:10 to 1:200, and more preferably 1:0 to 1:100, for example, 1:1, 1:5, 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, 1:110, 1:120, 1:130, 1:140, 1:150, 1:160, 1:170, 1:180, 1:190 or 1:200.

[0054] According to an embodiment of the present invention, in method A, the shearing speed of the crushing device is 500-20000 rpm, preferably 1500-8000 rpm, and more preferably 1500-3000 rpm.

[0055] According to an embodiment of the present invention, in method A, the addition of the biomass solution and coagulation bath to the crushing device includes the following steps: adding the biomass solution and coagulation bath to a crushing device such as a colloid mill, homogenizer or ball mill at the above volume ratio, and crushing the biomass solution and coagulation bath while mixing to form a micro-nano structure, thereby obtaining the biomass-based material.

[0056] According to an embodiment of the present invention, the temperature for dissolving the biomass is room temperature to 160°C, preferably 50-120°C, and more preferably 60-90°C.

[0057] According to an embodiment of the present invention, the dissolution time of the biomass is 0.5-6 hours, preferably 0.5-3 hours, and more preferably 1-2 hours.

[0058] According to an embodiment of the present invention, the dissolution of the biomass is carried out under stirring, microwave or ultrasonic conditions.

[0059] According to an embodiment of the present invention, the biomass is derived from one, two or more of the following substances: cellulose or its derivatives, starch or its derivatives, chitosan or its derivatives, chitin, alginate, lignin, dextran, hemicellulose, straw, plant stems and leaves, reeds, bagasse, Chinese medicine residue, tea residue, corn cob, fruit shell, vines, and branches.

[0060] For example, the cellulose derivative includes one or more of the following substances: carboxymethyl cellulose, cellulose acetate, cellulose nitrate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methyl cellulose.

[0061] For example, the starch derivative includes one of the following substances: carboxymethyl starch; for example, the chitosan derivative includes one of the following substances: carboxymethyl chitosan.

[0062] For example, the cellulose is selected from one, two or more of microcrystalline cellulose, cotton pulp, refined cotton, defatted cotton, wood pulp, cotton linters, bamboo pulp, straw pulp, bacterial cellulose and low-quality cellulose.

[0063] According to an embodiment of the present invention, the starch is selected from one, two or more of the following: soluble starch, amylopectin, high amylose, amylose, mung bean starch, potato starch, wheat starch, sweet potato starch, water chestnut starch, lotus root starch, water caltrop starch, corn starch, tapioca starch, sweet potato starch, kudzu starch, cassava starch, coconut starch, crystal starch, and cornstarch.

[0064] According to an embodiment of the present invention, the biomass is selected from at least one of microcrystalline cellulose, bacterial cellulose, lignin, cotton pulp, wood pulp, bamboo pulp, straw pulp, refined cotton, defatted cotton, cotton linters, sugarcane bagasse, wood, and straw; preferably one or more of microcrystalline cellulose, refined cotton, defatted cotton, and wood pulp.

[0065] Preferably, the lignin may be selected from one or more of syringyl lignin, guaiacyl lignin, and p-hydroxyphenyl lignin; or, the lignin may be selected from one or more of alkaline lignin, acidic lignin, dealkalized lignin, and organic solvent-soluble lignin.

[0066] The low-quality cellulose is plant tissue containing at least cellulose and lignin, such as herbaceous plants and / or agricultural and forestry waste.

[0067] For example, the herbaceous plant is selected from one or more of trees, shrubs, vines, leaves, and bamboo.

[0068] For example, the agricultural and forestry waste is selected from one or more of the following: tree bark, leaves, sawdust, crop straw, fruit shells or kernels, corn cobs, sugarcane bagasse, etc.

[0069] Preferably, the straw can be selected from one or more of wheat straw, rice straw, corn straw, soybean straw, cotton straw, ginger stalks, and sesame straw.

[0070] According to embodiments of the present invention, the solvent for dissolving biomass can be selected from any excellent solvent known in the art capable of completely dissolving biomass. Preferably, depending on the type of cellulose or cellulose-containing raw material, the selected solvent can be selected from one or more of the following systems: organic solvents, ionic liquids, mixed solvents of ionic liquids and organic solvents, choline-type ionic liquid eutectic solvent systems, organic solvent / salt systems, amine oxide systems (NMMO), urethane systems, alkali / water systems, alkali / urea systems, alkali / thiourea systems, liquid ammonia / NH4SCN, organic acids, aqueous solutions of metal salts, alcoholic solutions of metal hydrates, and aqueous-alcoholic mixed solutions of metal hydrates, etc.

[0071] The organic solvent may be selected from one or more of N,N-dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N-methylimidazolium, imidazolium, pyridine, ethylenediamine, hexafluoroacetone, hexafluoroisopropanol, glycerol, methyl isobutyl ketone, tetrahydrofuran, dioxane, and γ-valerol (GVL).

[0072] The organic solvent / salt system may be selected from one or more of the following: N,N-dimethylacetamide / lithium chloride (DMAc / LiCl) system, N-methyl-2-pyrrolidone / NMP, and N,N-dimethyl sulfoxide / tetrabutylamine fluoride system (DMSO / TBAF).

[0073] The alkali / water system can be selected from one or both of NaOH / H2O and KOH / H2O.

[0074] The alkali / urea system can be selected from NaOH / Urea.

[0075] The alkaline / thiourea system is selected from NaOH / thiourea.

[0076] The organic acid may be selected from one or more of formic acid, acetic acid, propionic acid, butyric acid, succinic acid, lactic acid, glutamic acid, glycine, dichloroacetic acid, trichloroacetic acid, and benzylsulfonic acid.

[0077] The aqueous solution of the metal salt is preferably an aqueous solution of metal salts such as CaCl2, ZnCl2, LiClO4, Ca(SCN)2, and LiSCN.

[0078] The alcoholic solution of the metal hydrate can be selected from a methanol solution of CaBr2·H2O or a methanol solution of CaCl2·2H2O.

[0079] The aqueous-alcoholic mixed solution of the metal hydrate can be selected from the methanol aqueous solution of CaBr2·H2O or the methanol aqueous solution of CaCl2·2H2O.

[0080] The amine oxide system can be an NMMO / H2O / DMSO system, an NMMO / H2O / diethyltriamine system, or an NMMO / H2O system.

[0081] The ionic liquid is selected from organic molten salts formed by cations and anions with a melting point below 100°C, and is preferably an organic molten salt capable of dissolving the biomass natural polymer.

[0082] For example, the cation of the ionic liquid is selected from one or more of substituted or unsubstituted imidazole, pyridine, pyrrole, amine, phosphine, choline, diazabicyclic, and amino acid-type cations; for example, the substituent can be C. 1-6 Alkyl, C 1-6 One or more of alkenyl, phenyl, or substituted phenyl groups; preferably one or more of methyl, ethyl, butyl, and allyl groups;

[0083] Preferably, the cation is selected from one or more of the following cations: 1-ethyl-3-methylimidazolium cation ([EMIM]), 3-methylimidazolium cation ([MIM]), 1-propyl-3-methylimidazolium cation ([PMIM]), 1-allyl-3-methylimidazolium cation ([AMIM]), 1-butyl-3-methylimidazolium cation ([BMIM]), 1-butyl-2,3-dimethylimidazolium cation ([BMMIM]), 1,3-dimethylimidazolium cation ([MMIM]), 1-methoxyethyl-3-methylimidazolium cation ([MeOEMIM]), 1-methoxymethyl-3-methylimidazolium cation ([MeOMMIM]), 1-hydroxy-3-methylimidazolium cation ([HMIM]), 1-(2-hydroxyethyl)-3-methylimidazolium cation ([HOEMIM]), 1-methyl-3-benzylmethylimidazolium cation ([MBzIM]), 1 The following cations are listed: pentyl-3-methylimidazolium cation ([PeMIM]), 1-benzyl-3-methylimidazolium cation ([BzMIM]), 1-m-methoxybenzyl-3-methylimidazolium cation ([MeOBzMIM]), 1-m-methylbenzyl-3-methylimidazolium cation ([MeBzMIM]), N-methylpyridine cation ([MPyr]), N-ethylpyridine cation ([EPyr]), N-butylpyridine cation ([BPyr]), N-hexylpyridine cation ([HPyr]), 1-butyl-3-methylpyrrolidone ion ([BMPyrr]), tris(2-hydroxyethyl)methylamine ([THEMA]), tetrabutylamine ([TBA]), tetrabutylphosphine ([PBu4]), glycine cation ([Gly]), choline cation ([Ch]), and 1,5-diazazobicyclo[4.3.0]one-5-ene ([DBNH]).

[0084] More preferably, the cation is selected from one or more of the following cations: 1-ethyl-3-methylimidazolium cation ([EMIM]), 1-allyl-3-methylimidazolium cation ([AMIM]), 1-butyl-3-methylimidazolium cation ([BMIM]), and choline cation ([Ch]).

[0085] For example, the anion is selected from one or more of the following: halogen anions, organic acid radicals, organic acid ester anions, and amino acid anions.

[0086] Preferably, the anion shown is selected from one or more of the following anions: chloride ion ([Cl]), bromide ion ([Br]), fluoride ion ([F]), formate ion ([HCOO]), acetate ion ([CH3COO] or [Ac]), glycolate ion ([HOCH2COO]), propionate ion ([CH3CH2COO] or [OPr]), butyrate ion ([CH3CH2CH2COO] or [OBu]), octanoate ion ([Oct]), benzoate ion ([C6H5COO] or [PhCOO]), lactate ion ([CH3CH(OH)COO] or [Lac]), and thioglycolate ion ([HSCH2COO]). The anions include one or more of the following: hexafluorophosphate ([PF6]), trifluoroborate ([BF3]), methyl phosphate ([(MeO)HPO2] or [MP]), dimethyl phosphate ([(MeO)2PO2] or [DMP]), diethyl phosphate ([(EtO)2PO2] or [DEP]), methanesulfonate anion ([MeOSO3]), trifluoromethanesulfonate anion ([CF3SO3]), glycine anion ([Gly]), lysine anion ([Lys]), valine anion ([Val]), dicyandiamide anion ([N(CN)2] or [DCA]), and bis(trifluoromethanesulfonylimide) ([Tf2N]).

[0087] More preferably, the anion is selected from one or more of the following anions: chloride ion ([Cl]), formate ion ([HCOO]), acetate ion ([Ac]), methyl phosphate ion ([(MeO)HPO2] or [MP]), dimethyl phosphate ion ([(MeO)2PO2] or [DMP]) and dicyandiamide anion ([N(CN)2] or [DCA]).

[0088] According to the present invention, the ionic liquid may be selected from one or more of the following ionic liquids: 1-ethyl-3-methylimidazolium chloride ionic liquid ([EMIM][Cl]), 1-ethyl-3-methylimidazolium bromide ionic liquid ([EMIM][Br]), 1-ethyl-3-methylimidazolium formate ionic liquid ([EMIM][HCOO]), 1-ethyl-3-methylimidazolium acetate ionic liquid ([EMIM][Ac]), 1-ethyl-3-methylimidazolium octanoate ionic liquid ([EMIM][Oct]), 1-ethyl-3-methylimidazolium methyl phosphate ionic liquid ([EMIM][MP]), 1-ethyl-3-methylimidazolium dimethyl phosphate ionic liquid ([EMIM][MP]), 1-ethyl-3-methylimidazolium dimethyl phosphate ionic liquid ([EMIM][Cl]), 1-ethyl-3-methylimidazolium dimethyl phosphate ionic liquid ([EMIM][CLOOD]), 1-ethyl-3-methylimidazolium octanoate ionic liquid ([EMIM][Oct]), 1-ethyl-3-methylimidazolium methyl phosphate ionic liquid ([EMIM][MP]), 1-ethyl-3-methylimidazolium dimethyl phosphate ionic liquid ([EMIM][CLOOD]), 1-ethyl-3-methylimidazolium dimethyl phosphate ionic liquid ([EMIM][CLOOD]), 1-ethyl-3-methylimidazolium dimethyl phosphate ionic liquid ([EMIM][CLOOD]), 1-ethyl-3-methylimidazolium ... [EMIM][DMP]), 1-ethyl-3-methylimidazolium diethyl phosphate ionic liquid ([EMIM][DEP]), 1-ethyl-3-methylimidazolium propionate ionic liquid ([EMIM][OPr]), 1-ethyl-3-methylimidazolium octate ionic liquid ([EMIM][OBu]), 1-ethyl-3-methylimidazolium glycinate ionic liquid ([EMIM][Gly]), 1-ethyl-3-methylimidazolium lysine ionic liquid ([EMIM][Lys]), 1-allyl-3-methylimidazolium chloride ionic liquid ([AMIM][Cl]), 1-allyl-3-methylimidazolium bromide ionic liquid ([AMIM][Br]), 1-ene 1-Butyl-3-methylimidazolium carbamate ionic liquid ([AMIM][HCOO]), 1-allyl-3-methylimidazolium acetate ionic liquid ([AMIM][Ac]), 1-butyl-3-methylimidazolium chloride ionic liquid ([BMIM][Cl]), 1-butyl-3-methylimidazolium bromide ionic liquid ([BMIM][Br]), 1-butyl-3-methylimidazolium carbamate ionic liquid ([BMIM][HCOO]), 1-butyl-3-methylimidazolium acetate ionic liquid ([BMIM][Ac]), 1-butyl-3-methylimidazolium hydroxyacetate ionic liquid ([BMIM][HOCH2COO]), 1-butyl-3-methylimidazolium propionate ionic liquid The following ionic liquids are available: [BMIM][CH3CH2COO], [BMIM][Lac], [BMIM][CH3CH2CH2COO], [BMIM][C6H5COO], [BMIM][H2NCH2COO], [BMIM][N(CN)2], and [BMIM][Tf2N].1-Butyl-3-methylimidazolium hexafluorophosphate ionic liquid ([BMIM][PF6]), 1-Butyl-3-methylimidazolium tetrafluoroborate ionic liquid ([BMIM][BF4]), 1-Butyl-3-methylimidazolium methanesulfonate ionic liquid ([BMIM][MeOSO3]), 1-Butyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid ([BMIM][CF3SO3]), 1-Butyl-2,3-dimethylimidazolium tetrafluoroborate ionic liquid ([BMMIM][BF4]), 3-methylimidazolium formate ionic liquid ([MIM][HCOO]), 1,3-dimethylimidazolium chloride ionic liquid ([MMIM][Cl]), 1,3-dimethylimidazolium chloride ionic liquid ([MMIM][Cl]), 1,3-dimethylimidazolium chloride... 1,3-Dimethylimidazolium methyl phosphate ionic liquid ([MMIM][MP]), 1,3-dimethylimidazolium dimethyl phosphate ionic liquid ([MMIM][DMP]), 1,3-dimethylimidazolium methanesulfonate ionic liquid ([MMIM][MeOSO3]), 1-hydroxy-3-methylimidazolium chloride ionic liquid ([HMIM][Cl]), 1-hydroxy-3-methylimidazolium trifluoromethyl sulfonate ionic liquid ([HMIM][CF3SO3]), 1-(2-hydroxyethyl)-3-methylimidazolium chloride ionic liquid ([HOEMIM][Cl]), 1-methoxymethyl-3-methylimidazolium bromide ionic liquid ([MeOMMIM][Br]), 1-methoxyethyl N-methyl-3-methylimidazolium bromide ionic liquid ([MeOEMIM][Br]), N-ethylpyridine chloride ionic liquid ([EPyr][Cl]), N-ethylpyridine bromide ionic liquid ([EPyr][Br]), N-methylpyridine carboxylate ionic liquid ([MPyr][HCOO]), tris(2-hydroxyethyl)methylamine acetate ionic liquid ([THEMA][Ac]), tris(2-hydroxyethyl)methylamine methanesulfonate ionic liquid ([THEMA][MeOSO3]), tris(2-hydroxyethyl)methylamine trifluoromethanesulfonate ionic liquid [THEMA][CF3SO3], tetrabutylphosphine valine ionic liquid [PBu4][Val], tetrabutylphosphine lis Amino acid salt ionic liquids [PBu4][Lys], tetrabutylphosphine glycine salt ionic liquid [PBu4][Gly], 1-benzyl-3-methylimidazolium chloride ionic liquid ([BzMIM][Cl]), 1-benzyl-3-methylimidazolium dicyandiamide salt ionic liquid ([BzMIM][DCA]), 1-m-methylbenzyl-3-methylimidazolium chloride ionic liquid ([MeBzMIM][Cl]), 1-m-methoxybenzyl-3-methylimidazolium chloride ionic liquid ([MeOBzMIM][Cl]), choline chloride ionic liquid ([Ch][Cl]), choline bromide ionic liquid (Ch][Br]), and choline acetate ionic liquid ([Ch][CH3COO]).Ionic liquids include propionic choline ([Ch][CH3CH2COO]), butyrate choline ([Ch][CH3CH2CH2COO]), glycine hydrochloride ([Gly][Cl]), and 1,5-diazabicyclo[4.3.0]ketone-5-ene acetate ([DBNH][Ac]).

[0089] Preferably, the choline-type eutectic solvent system is selected from one or more of [Ch][Cl] / urea, [Ch][Br] / urea, [Ch][Cl] / thio-urea, [Ch][Cl] / glycerol, and [Ch][Cl] / lactic acid.

[0090] Preferably, the solvent system for dissolving cellulose or cellulose-containing raw materials is selected from the ionic liquid and / or the NaOH / Urea system; more preferably, the ionic liquid for dissolving cellulose or cellulose-containing raw materials is selected from one or more of [AMIM][Cl], [BMIM][Cl], [EMIM][Ac], and [BMIM][Ac].

[0091] According to an embodiment of the present invention, the coagulation bath is selected from at least one of water, alcohol, an alcohol-water mixture, an aqueous HCl solution, an aqueous NaOH solution, and an aqueous solution of an inorganic salt, preferably water and / or alcohol, such as water. The alcohol is, for example, at least one of methanol, ethanol, ethylene glycol, propanol, glycerol, isopropanol, n-butanol, and isobutanol, preferably methanol, ethanol, or ethylene glycol, with ethanol being an example. Further, the ratio of alcohol to water in the alcohol-water mixture is not particularly limited, for example, it can be (1-10):(1-10), preferably 1:(1-10), with examples of 1:2, 1:3, 1:4, 1:5, and 1:10. Exemplarily, the inorganic salt can be selected from at least one of Na₂SO₄, NaCl, KCl, CaCl₂, MgCl₂, FeCl₃, KNO₃, and NaNO₃.

[0092] [Biomass-based emulsion]

[0093] A biomass-based emulsion, the biomass-based emulsion comprising a biomass-based material and a biowax, wherein the biomass-based material comprises a micron-scale structure and a nano-scale structure distributed on the micron-scale structure.

[0094] According to an embodiment of the present invention, the biomass-based material is prepared by the above method.

[0095] According to an embodiment of the present invention, in the biomass-based emulsion, the mass ratio of the biomass-based material to the biowax is (0.01-10):(0.1-50), for example, 1.6:20, 0.96:4, 1.8:10, 1.98:1, 3:40, 2.94:2, 0.95:5, 0.8:20, 1.8:10, 0.9:10, 0.95:5, 0.9:10, or 3:40.

[0096] According to an embodiment of the present invention, the biomass-based emulsion has stability.

[0097] According to an embodiment of the present invention, the biomass-based emulsion further includes a dispersing agent.

[0098] According to an embodiment of the present invention, the dispersing agent may be selected from water and / or alcohol.

[0099] According to an embodiment of the present invention, the biowax has low surface energy and is hydrophobic.

[0100] According to an embodiment of the present invention, the biowax is selected from at least one of animal wax and plant wax.

[0101] In this invention, the animal wax or plant wax may be any animal wax or plant wax known in the art. Preferably, the animal wax is selected from at least one of beeswax and wool wax. Preferably, the plant wax is selected from at least one of palm wax, sugarcane wax, candelilla wax, soybean wax, coconut wax, rice bran wax, and ice flower wax.

[0102] According to an embodiment of the present invention, the biowax particles have a micron particle size.

[0103] According to an embodiment of the present invention, the particle size of the biowax is 1μm-500μm, for example, 10μm, 20μm, 30μm, 40μm, 50μm, 60μm, 70μm, 80μm, 90μm, 100μm, 150μm, 200μm, 300μm, 400μm, or 500μm.

[0104] According to an embodiment of the present invention, the melting point of the bio-wax is selected from bio-waxes with a melting point below 100°C, preferably bio-waxes with a melting point between 60 and 90°C, for example, 70°C or 80°C. Further, the bio-wax is selected, for example, from beeswax (melting point 62-67°C), wool wax (43-55°C), rice bran wax (60-85°C), palm wax (80-86°C), sugarcane wax (70-84°C), and candelilla wax (67-71°C).

[0105] According to a preferred embodiment of the present invention, the biomass-based emulsion comprises biomass-based materials, biowax, and dispersing agents, wherein the biowax and dispersing agents have the meanings described above.

[0106] According to an embodiment of the present invention, the biomass-based material is a recycled natural polymer (e.g., type II cellulose, or a mixture of type II cellulose and type I cellulose), wherein the recycled natural polymer includes a micron-scale structure and a nano-scale structure distributed on the micron-scale structure.

[0107] According to an embodiment of the present invention, the size (i.e., the average volume size) of the micron-scale structure is 10μm to 100μm, preferably 20μm to 70μm, and more preferably 30μm to 50μm, for example, any value among 10μm, 20μm, 30μm, 40μm, 50μm, 60μm, 70μm, 80μm, 90μm, and 100μm, or any point value among any two intermediate values.

[0108] According to an embodiment of the present invention, the size (i.e., the volume average size) of the micron-scale structure is 10 μm to 300 μm, preferably 50 μm to 250 μm, and more preferably 100 μm to 200 μm, for example, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm, 12 Any value from 5μm, 130μm, 135μm, 140μm, 145μm, 150μm, 155μm, 160μm, 165μm, 170μm, 175μm, 180μm, 185μm, 190μm, 195μm, 200μm, 210μm, 220μm, 230μm, 240μm, 250μm, 260μm, 270μm, 280μm, 290μm, 300μm, or any point value from the intermediate values ​​formed by any two points.

[0109] According to an embodiment of the present invention, the length of the nanoscale structure is 500nm to 1500nm, preferably 700nm to 1200nm, and more preferably 800nm ​​to 1000nm, for example, any value or any intermediate value among 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, 1100nm, 1200nm, 1300nm, 1400nm, and 1500nm.

[0110] According to an embodiment of the present invention, the diameter of the nanoscale structure is 200nm to 600nm, preferably 300nm to 500nm, for example, any value among 200nm, 300nm, 400nm, 500nm, and 600nm, or any intermediate value formed by any two of these values.

[0111] According to an embodiment of the present invention, the aspect ratio of the nanoscale structure is 1:1 to 1:150, preferably 1:1 to 1:100, and more preferably 1:10 to 1:100, for example 1:50.

[0112] According to an embodiment of the present invention, the micron-level structure includes at least one of micron-sheets, micron-fibers, and micron-level structures.

[0113] According to an embodiment of the present invention, the micron-scale structure is fibrous or membrane-like, and may also be referred to as broom-like.

[0114] According to an embodiment of the present invention, the nanoscale structure is distributed on the surface and / or edges of the micrometer-scale structure. Specifically, the nanoscale structure is densely distributed on the surface and / or edges of the micrometer-scale structure.

[0115] According to an embodiment of the present invention, the nanoscale structure is distributed on a micrometer-scale structure and thus forms a flocculent structure as a whole.

[0116] According to an embodiment of the present invention, the nanoscale structure is distributed on a micrometer-scale structure and thus forms an integral structure similar to a porous sponge.

[0117] According to an embodiment of the present invention, the nanoscale structure and the micrometer-scale structure together form a feather-like structure.

[0118] According to an embodiment of the present invention, the nanoscale structure is in the form of a villous, tentacle-like, whisker-like, or other irregular structure.

[0119] According to an embodiment of the present invention, the biomass-based material has a fibrous, sheet-like, feather-like, branch-like, flocculent, or porous sponge-like structure.

[0120] A biomass-based emulsion, comprising a surface-modified biomass-based material and a biowax, wherein the surface-modified biomass-based material is a surface-modified version of the aforementioned biomass-based material; or a material prepared by the aforementioned method for preparing biomass-based materials, except that the raw biomass is replaced with surface-modified biomass.

[0121] According to an embodiment of the present invention, the surface modification may be surface cationization modification, surface anionization modification, or surface hydrophobic treatment.

[0122] According to an embodiment of the present invention, the surface-modified biomass-based material has the same structure as the biomass-based material.

[0123] According to an embodiment of the present invention, in the biomass-based emulsion, the mass ratio of the surface-modified biomass-based material to the biowax is (0.01-10):(0.1-50), for example, 1.6:20, 0.96:4, 1.8:10, 1.98:1, 3:40, 2.94:2, 0.95:5, 0.8:20, 1.8:10, 0.9:10, 0.95:5, 0.9:10, or 3:40.

[0124] According to an embodiment of the present invention, the biomass-based emulsion has stability.

[0125] According to an embodiment of the present invention, the biomass-based emulsion further includes a dispersing agent.

[0126] According to an embodiment of the present invention, the dispersing agent may be selected from water and / or alcohol.

[0127] According to an embodiment of the present invention, the biowax has low surface energy and is hydrophobic.

[0128] According to an embodiment of the present invention, the biowax is selected from at least one of animal wax and plant wax.

[0129] In this invention, the animal wax or plant wax may be any animal wax or plant wax known in the art. Preferably, the animal wax is selected from at least one of beeswax and wool wax. Preferably, the plant wax is selected from at least one of palm wax, sugarcane wax, candelilla wax, soybean wax, coconut wax, rice bran wax, and ice flower wax.

[0130] According to an embodiment of the present invention, the biowax particles have a micron particle size.

[0131] According to an embodiment of the present invention, the particle size of the biowax is 1μm-500μm, for example, 10μm, 20μm, 30μm, 40μm, 50μm, 60μm, 70μm, 80μm, 90μm, 100μm, 150μm, 200μm, 300μm, 400μm, or 500μm.

[0132] According to an embodiment of the present invention, the melting point of the bio-wax is selected from bio-waxes with a melting point below 100°C, preferably bio-waxes with a melting point between 60 and 90°C, for example, 70°C or 80°C. Further, the bio-wax is selected, for example, from beeswax (melting point 62-67°C), wool wax (43-55°C), rice bran wax (60-85°C), palm wax (80-86°C), sugarcane wax (70-84°C), and candelilla wax (67-71°C).

[0133] According to a preferred embodiment of the present invention, the biomass-based emulsion comprises a surface-modified biomass-based material, a biowax, and a dispersing agent, wherein the biowax and the dispersing agent have the meanings described above.

[0134] A biomass-based emulsion, comprising a substituted biomass-based material and a biowax, wherein the substituted biomass-based material is a substitute for the aforementioned biomass-based material; or it is a material prepared by the aforementioned method for preparing biomass-based materials, except that the raw biomass is replaced with the substituted biomass.

[0135] According to an embodiment of the present invention, the substituted biomass-based material is a low-substituted biomass-based material. Preferably, the degree of substitution of the low-substituted biomass-based material is 0.0001 to 2.0, more preferably 0.001 to 1.8, for example 0.1, 0.5, 0.65, 0.86, 1.46, 1.6.

[0136] According to embodiments of the present invention, the substitution may be selected from one or more of esterification, acylation, etherification, amidation, or ammoniation.

[0137] According to embodiments of the present invention, the substitution can be prepared by reacting a functionalized derivatizing agent with a biomass-based material or biomass. For example, the functionalized derivatizing agent can be selected from esterification agents, acylation agents, etherification agents, ammoniation agents, and / or amidation agents.

[0138] According to an embodiment of the present invention, the substituted biomass-based material may be selected from cellulose acetate (e.g., cellulose acetate with a degree of substitution of 0.65, 0.86, 1.46, or 1.6) or cellulose-g-polylactic acid.

[0139] According to an embodiment of the present invention, in the biomass-based emulsion, the mass ratio of the substituted biomass-based material to the biowax is (0.01-10):(0.1-50), for example, 1.6:20, 0.96:4, 1.8:10, 1.98:1, 3:40, 2.94:2, 0.95:5, 0.8:20, 1.8:10, 0.9:10, 0.95:5, 0.9:10, or 3:40.

[0140] According to an embodiment of the present invention, the biomass-based emulsion has stability.

[0141] According to an embodiment of the present invention, the biomass-based emulsion further includes a dispersing agent.

[0142] According to an embodiment of the present invention, the dispersing agent may be selected from water and / or alcohol.

[0143] According to an embodiment of the present invention, the biowax has low surface energy and is hydrophobic.

[0144] According to an embodiment of the present invention, the biowax is selected from at least one of animal wax and plant wax.

[0145] In this invention, the animal wax or plant wax may be any animal wax or plant wax known in the art. Preferably, the animal wax is selected from at least one of beeswax and wool wax. Preferably, the plant wax is selected from at least one of palm wax, sugarcane wax, candelilla wax, soybean wax, coconut wax, rice bran wax, and ice flower wax.

[0146] According to an embodiment of the present invention, the biowax particles have a micron particle size.

[0147] According to an embodiment of the present invention, the particle size of the biowax is 1-500 μm, for example, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 150 μm, 200 μm, 300 μm, 400 μm, or 500 μm.

[0148] According to an embodiment of the present invention, the melting point of the bio-wax is selected from bio-waxes with a melting point below 100°C, preferably bio-waxes with a melting point between 60 and 90°C, for example, 70°C or 80°C. Further, the bio-wax is selected, for example, from beeswax (melting point 62-67°C), wool wax (43-55°C), rice bran wax (60-85°C), palm wax (80-86°C), sugarcane wax (70-84°C), and candelilla wax (67-71°C).

[0149] According to a preferred embodiment of the present invention, the biomass-based emulsion comprises a substitute biomass-based material, a biowax, and a dispersing agent, wherein the biowax and the dispersing agent have the meanings described above.

[0150] A biomass-based emulsion, comprising a biomass-based dispersion and a biowax, wherein the biomass-based dispersion comprises the aforementioned biomass-based material and a dispersing agent, wherein the biomass-based material and the biowax are dispersed in the dispersing agent, and the dispersing agent is a solvent system capable of continuously dispersing the biomass-based material and the biowax.

[0151] According to an embodiment of the present invention, the mass ratio of biomass-based material to biowax in the biomass-based emulsion is (0.01-10):(0.1-50), for example, 1.6:20, 0.96:4, 1.8:10, 1.98:1, 3:40, 2.94:2, 0.95:5, 0.8:20, 1.8:10, 0.9:10, 0.95:5, 0.9:10, 3:40.

[0152] According to an embodiment of the present invention, the biomass-based emulsion has stability.

[0153] According to an embodiment of the present invention, the biowax has low surface energy and is hydrophobic.

[0154] According to an embodiment of the present invention, the biowax is selected from at least one of animal wax and plant wax.

[0155] In this invention, the animal wax or plant wax may be any animal wax or plant wax known in the art. Preferably, the animal wax is selected from at least one of beeswax and wool wax. Preferably, the plant wax is selected from at least one of palm wax, sugarcane wax, candelilla wax, soybean wax, coconut wax, rice bran wax, and ice flower wax.

[0156] According to an embodiment of the present invention, the biowax particles have a micron particle size.

[0157] According to an embodiment of the present invention, the particle size of the biowax is 1-500 μm, for example, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 150 μm, 200 μm, 300 μm, 400 μm, or 500 μm.

[0158] According to an embodiment of the present invention, the melting point of the bio-wax is selected from bio-waxes with a melting point below 100°C, preferably bio-waxes with a melting point between 60 and 90°C, for example, 70°C or 80°C. Further, the bio-wax is selected, for example, from beeswax (melting point 62-67°C), wool wax (43-55°C), rice bran wax (60-85°C), palm wax (80-86°C), sugarcane wax (70-84°C), and candelilla wax (67-71°C).

[0159] According to an embodiment of the present invention, the biomass-based material exists in the form of a microgel in the biomass-based emulsion.

[0160] According to an embodiment of the present invention, hydroxyl groups are distributed on the micron-scale and / or nano-scale structures of the biomass-based material, and the micron-scale structures and nano-scale structures, or the micron-scale structures, nano-scale structures and fluids, form a gel network through hydrogen bonds to form a microgel.

[0161] According to embodiments of the present invention, the dispersing agent is selected from at least one of water, alcohol, an alcohol-water mixture, an aqueous HCl solution, an aqueous NaOH solution, and an aqueous solution of an inorganic salt. Preferably, the dispersing agent is selected from water and / or alcohol, such as water. Exemplarily, the alcohol is selected from at least one of methanol, ethanol, ethylene glycol, propanol, glycerol, isopropanol, n-butanol, and isobutanol, preferably at least one of methanol, ethanol, and ethylene glycol, such as ethanol. Exemplarily, the inorganic salt may be selected from at least one of Na₂SO₄, NaCl, KCl, CaCl₂, MgCl₂, FeCl₃, KNO₃, and NaNO₃.

[0162] According to an embodiment of the present invention, the biomass-based material has a mass fraction of 0.050-95 wt.% in the emulsion.

[0163] According to an embodiment of the present invention, the biomass-based emulsion is transparent, milky white, light brown, or light yellow.

[0164] A biomass-based emulsion, the biomass-based emulsion comprising a surface-modified biomass-based dispersion and a biowax, the surface-modified biomass-based dispersion comprising the aforementioned surface-modified biomass-based material and a dispersing agent, the surface-modified biomass-based material and the biowax being dispersed in the dispersing agent, the dispersing agent being a solvent system capable of continuously dispersing the surface-modified biomass-based material and the biowax.

[0165] According to an embodiment of the present invention, in the biomass-based emulsion, the mass ratio of surface-modified biomass-based material to biowax is (0.01-10):(0.1-50), for example, 1.6:20, 0.96:4, 1.8:10, 1.98:1, 3:40, 2.94:2, 0.95:5, 0.8:20, 1.8:10, 0.9:10, 0.95:5, 0.9:10, 3:40.

[0166] According to an embodiment of the present invention, the biomass-based emulsion has stability.

[0167] According to an embodiment of the present invention, the biowax has low surface energy and is hydrophobic.

[0168] According to an embodiment of the present invention, the biowax is selected from at least one of animal wax and plant wax.

[0169] In this invention, the animal wax or plant wax may be any animal wax or plant wax known in the art. Preferably, the animal wax is selected from at least one of beeswax and wool wax. Preferably, the plant wax is selected from at least one of palm wax, sugarcane wax, candelilla wax, soybean wax, coconut wax, rice bran wax, and ice flower wax.

[0170] According to an embodiment of the present invention, the biowax particles have a micron particle size.

[0171] According to an embodiment of the present invention, the particle size of the biowax is 1-500 μm, for example, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 150 μm, 200 μm, 300 μm, 400 μm, or 500 μm.

[0172] According to an embodiment of the present invention, the melting point of the bio-wax is selected from bio-waxes with a melting point below 100°C, preferably bio-waxes with a melting point between 60 and 90°C, for example, 70°C or 80°C. Further, the bio-wax is selected, for example, from beeswax (melting point 62-67°C), wool wax (43-55°C), rice bran wax (60-85°C), palm wax (80-86°C), sugarcane wax (70-84°C), and candelilla wax (67-71°C).

[0173] According to an embodiment of the present invention, the dispersing agent in the surface-modified biomass-based emulsion has the definition described above, and is preferably water and / or alcohol.

[0174] According to an embodiment of the present invention, in the surface-modified biomass-based emulsion, the surface-modified biomass-based material exists in the form of a microgel.

[0175] According to an embodiment of the present invention, hydroxyl groups are distributed on the micron-scale and / or nano-scale structures of the surface-modified biomass-based material, and the micron-scale structures and nano-scale structures, or the micron-scale structures, nano-scale structures and fluids, form a gel network through hydrogen bonds to form a microgel.

[0176] A biomass-based emulsion, the biomass-based emulsion comprising a substituted biomass-based dispersion and a biowax, the substituted biomass-based dispersion comprising the aforementioned substituted biomass-based material and a dispersing agent, the substituted biomass-based material and the biowax being dispersed in the dispersing agent, the dispersing agent being a solvent system capable of continuously dispersing the substituted biomass-based material and the biowax.

[0177] According to an embodiment of the present invention, in the biomass-based emulsion, the mass ratio of the substituted biomass-based material to the biowax is (0.01-10):(0.1-50), for example, 1.6:20, 0.96:4, 1.8:10, 1.98:1, 3:40, 2.94:2, 0.95:5, 0.8:20, 1.8:10, 0.9:10, 0.95:5, 0.9:10, 3:40.

[0178] According to an embodiment of the present invention, the biomass-based emulsion has stability.

[0179] According to an embodiment of the present invention, the biowax has low surface energy and hydrophobicity.

[0180] According to an embodiment of the present invention, the biowax is selected from at least one of animal wax and plant wax.

[0181] In this invention, the animal wax or plant wax may be any animal wax or plant wax known in the art. Preferably, the animal wax is selected from at least one of beeswax and wool wax. Preferably, the plant wax is selected from at least one of palm wax, sugarcane wax, candelilla wax, soybean wax, coconut wax, rice bran wax, and ice flower wax.

[0182] According to an embodiment of the present invention, the biowax particles have a micron particle size.

[0183] According to an embodiment of the present invention, the particle size of the biowax is 1-500 μm, for example, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 150 μm, 200 μm, 300 μm, 400 μm, or 500 μm.

[0184] According to an embodiment of the present invention, the melting point of the bio-wax is selected from bio-waxes with a melting point below 100°C, preferably bio-waxes with a melting point between 60 and 90°C, for example, 70°C or 80°C. Further, the bio-wax is selected, for example, from beeswax (melting point 62-67°C), wool wax (43-55°C), rice bran wax (60-85°C), palm wax (80-86°C), sugarcane wax (70-84°C), and candelilla wax (67-71°C).

[0185] According to an embodiment of the present invention, the dispersant of the substituted biomass-based emulsion has the meaning as described above, and is preferably water and / or alcohol.

[0186] According to an embodiment of the present invention, the content of the substituted biomass-based material in the substituted biomass-based emulsion can be 0.050-95 wt.%; for example, it can be 0.5-10 wt.%.

[0187] According to an embodiment of the present invention, the substituted biomass-based emulsion is a micro / nano emulsion; specifically, in the emulsion, the substituted biomass-based material exists in the form of a microgel.

[0188] According to an embodiment of the present invention, hydroxyl groups are distributed on the micron-scale and / or nano-scale structures of the biomass-based material, and the micron-scale structures and nano-scale structures, or the micron-scale structures, nano-scale structures and fluids, form a gel network through hydrogen bonds to form a microgel.

[0189] A biomass-based emulsion, comprising a multi-component biomass-based dispersion and a biowax; the continuous phase of the biomass-based emulsion is a dispersing agent; the dispersed phase of the biomass-based emulsion contains a biowax, a functional component, and at least one of the following components 1) to 3):

[0190] 1) The above-mentioned biomass-based materials;

[0191] 2) The above-mentioned alternative biomass-based materials;

[0192] 3) The above-mentioned surface-modified biomass-based materials.

[0193] According to an embodiment of the present invention, in the biomass-based emulsion, the mass ratio of at least one of components 1) to 3) to biowax is (0.01 to 10): (0.1 to 50), for example, 1.6:20, 0.96:4, 1.8:10, 1.98:1, 3:40, 2.94:2, 0.95:5, 0.8:20, 1.8:10, 0.9:10, 0.95:5, 0.9:10, or 3:40.

[0194] According to an embodiment of the present invention, the biomass-based emulsion has stability.

[0195] According to an embodiment of the present invention, the biowax has low surface energy and hydrophobicity.

[0196] According to an embodiment of the present invention, the biowax is selected from at least one of animal wax and plant wax.

[0197] In this invention, the animal wax or plant wax may be any animal wax or plant wax known in the art. Preferably, the animal wax is selected from at least one of beeswax and wool wax. Preferably, the plant wax is selected from at least one of palm wax, sugarcane wax, candelilla wax, soybean wax, coconut wax, rice bran wax, and ice flower wax.

[0198] According to an embodiment of the present invention, the biowax particles have a micron particle size.

[0199] According to an embodiment of the present invention, the particle size of the biowax is 1-500 μm, for example, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 150 μm, 200 μm, 300 μm, 400 μm, or 500 μm.

[0200] According to an embodiment of the present invention, the melting point of the bio-wax is selected from bio-waxes with a melting point below 100°C, preferably bio-waxes with a melting point between 60 and 90°C, for example, 70°C or 80°C. Further, the bio-wax is selected, for example, from beeswax (melting point 62-67°C), wool wax (43-55°C), rice bran wax (60-85°C), palm wax (80-86°C), sugarcane wax (70-84°C), and candelilla wax (67-71°C).

[0201] According to an embodiment of the present invention, the dispersing agent in the multi-component biomass-based emulsion has the selections shown above, preferably water and / or alcohol.

[0202] According to an embodiment of the present invention, the functional component is selected from one or more of the following substances: nanocellulose, carbon nanotubes, graphene, fullerene, carbon black, silver nanowires, quantum dots, carbon dots, nanoFe3O4, drugs, etc.

[0203] According to an embodiment of the present invention, the content of at least one of components 1) to 3) may be 0.050-95 wt.%; for example, it may be 0.5-10 wt.%.

[0204] According to an embodiment of the present invention, the multi-component biomass-based emulsion is a micro / nano emulsion; specifically, in the emulsion, at least one of components 1) to 3) exists in the form of a microgel.

[0205] According to an embodiment of the present invention, the above-mentioned biomass-based emulsion further includes adjuvants.

[0206] According to an embodiment of the present invention, the adjuvant is selected from adjuvants and dosages known in the art, and no specific limitation is made in the present invention.

[0207] The biomass-based emulsion of the present invention maintains high stability even after being left at room temperature for more than 3 months, and is minimally affected by dispersing agents (e.g., water hardness and electrolytes).

[0208] The above-mentioned biomass-based emulsion of the present invention has good formulation properties, wherein biomass-based materials, surface-modified biomass-based materials, and substituted biomass-based materials are easily compatible with various biowaxes and additives, and work together to form a product with excellent performance.

[0209] [Preparation method of biomass-based emulsion]

[0210] This invention also provides a method for preparing the above-mentioned biomass-based emulsion, wherein the preparation method is selected from method one or method two, wherein...

[0211] Method 1 includes: (I) mixing biowax with at least one of the following substances to obtain a mixture: biomass-based material, surface-modified biomass-based material, substituted biomass-based material, biomass-based dispersion, surface-modified biomass-based dispersion, substituted biomass-based dispersion, multi-component biomass-based dispersion;

[0212] (II) Heat the mixture from step (I) to above the melting point of the biowax (e.g., below 100°C, preferably between 60 and 90°C). After the biowax melts, mechanical emulsify it to obtain a uniformly dispersed water-in-wax emulsion.

[0213] (III) After cooling the water-in-wax emulsion from step (II) to room temperature, the biomass-based emulsion is obtained.

[0214] Method 2 includes: mixing biowax with at least one of the following substances to obtain a mixture: biomass-based material, surface-modified biomass-based material, substituted biomass-based material, biomass-based dispersion, surface-modified biomass-based dispersion, substituted biomass-based dispersion, multi-component biomass-based dispersion; and emulsifying the mixture by vortexing to obtain the biomass-based emulsion.

[0215] According to an embodiment of the present invention, in method two, the particle size of the biowax is not greater than 300 μm, for example, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 150 μm, 200 μm, or 300 μm.

[0216] According to an embodiment of the present invention, the mechanical emulsification refers to emulsifying in a high-speed disperser and / or homogenizer for a period of time, as long as a homogeneous water-in-wax emulsion can be obtained, for example, emulsifying for 1-60 minutes, or for example, emulsifying for 10-30 minutes.

[0217] According to an embodiment of the present invention, the vortex emulsification refers to mixing by shaking in a vortex pot.

[0218] According to an embodiment of the present invention, in method one or method two, each substance in the mixture and its amount have the meanings described above.

[0219] [Preparation method of biomass-based dispersion]

[0220] A method for preparing the above-mentioned biomass-based dispersion, selected from Scheme 1, Scheme 2, or Scheme 3:

[0221] Option 1: Dissolve biomass in a solvent to form a biomass solution. Add the biomass solution and coagulation bath to a crushing device for crushing. After filtration, wash with a dispersing agent to obtain a biomass-based dispersion.

[0222] Option 2: Dissolve biomass in a solvent to form a biomass solution, pour the biomass solution into a coagulation bath to form a biomass gel, wash the gel, and then further crush and homogenize it with a dispersing agent to obtain a biomass-based dispersion.

[0223] Option 3: Disperse the above-mentioned biomass-based materials in a dispersion reagent to form a biomass-based dispersion.

[0224] According to an embodiment of the present invention, the solvent, coagulation bath, and dispersing agent have the definitions described above.

[0225] According to an embodiment of the present invention, in Scheme 1, the volume ratio of the dispersing agent to the coagulation bath has the definition described above.

[0226] According to an embodiment of the present invention, Scheme 1 includes the following steps: dissolving biomass in a solvent to form a biomass solution, adding the biomass solution and a coagulation bath simultaneously into a crushing device for crushing, washing, and obtaining a biomass-based dispersion.

[0227] According to an embodiment of the present invention, embodiment two includes the following steps: dissolving biomass in a solvent to form a biomass solution, pouring the biomass solution into a coagulation bath, washing the formed biomass gel, and further crushing and homogenizing it with a dispersing agent to obtain a biomass-based dispersion.

[0228] According to an embodiment of the present invention, in embodiment three, dispersing the biomass-based material in the dispersion reagent includes the following steps: adding the biomass-based material to the dispersion reagent and mixing it evenly.

[0229] According to an embodiment of the present invention, the mixing can be carried out under stirring conditions.

[0230] [Preparation method of surface-modified biomass-based dispersion]

[0231] The present invention also provides a method for preparing the above-mentioned surface-modified biomass-based dispersion, comprising the following steps:

[0232] Surface-modified biomass is dissolved in a solvent to form a surface-modified biomass solution; the above surface-modified biomass solution and coagulation bath are added to a crushing device, and the two are crushed while being mixed to obtain the surface-modified biomass-based dispersion.

[0233] Alternatively, the above-mentioned surface-modified biomass solution can be poured into a coagulation bath, washed after forming a gel, and further crushed and homogenized with a dispersing agent to obtain the surface-modified biomass-based dispersion.

[0234] Alternatively, the biomass-based dispersion can be mixed with a modifying agent or obtained through surface chemical modification to obtain the surface-modified biomass-based dispersion.

[0235] According to an embodiment of the present invention, the surface-modified biomass-based material and the coagulation bath have the meanings described above.

[0236] According to an embodiment of the present invention, the modifying agent may be one or more of quaternary ammonium salts, sulfonates, phosphates, etc.; for example, sodium vinyl sulfonate or 3-chloro-2-hydroxypropyltrimethylammonium chloride.

[0237] According to an embodiment of the present invention, the surface-modified biomass-based material solution can be obtained by homogeneous chemical derivatization or functionalization of biomass-based material with a modifying reagent in the following solvent.

[0238] According to an embodiment of the present invention, the micro-nano solution of the surface-modified biomass-based material can be a biomass solution in which the surface-modified biomass-based material is completely dissolved or a heterogeneous dispersion in which the surface-modified biomass-based material is partially dissolved.

[0239] [Preparation method of biomass-based dispersant]

[0240] The present invention also provides a method for preparing the above-mentioned substituted biomass-based dispersion, comprising the following steps: dissolving substituted biomass in a solvent to form a substituted biomass solution; adding the above-mentioned substituted biomass solution and a coagulation bath into a crushing device, and crushing the two simultaneously to obtain the substituted biomass-based dispersion;

[0241] Alternatively, the above-mentioned substituted biomass solution is poured into a coagulation bath, and after forming a gel, it is washed and further crushed and homogenized with a dispersing agent to obtain the substituted biomass-based dispersion.

[0242] Alternatively, the biomass-based material dispersion can be mixed with a functionalized derivatizing agent and reacted to obtain the substituted biomass-based dispersion.

[0243] According to embodiments of the present invention, the substituted biomass-based material, coagulation bath, and functionalized derivatizing reagent have the meanings described above.

[0244] [Preparation method of multi-component biomass-based dispersion]

[0245] The present invention also provides a method for preparing the above-mentioned multi-component biomass-based dispersion, selected from Scheme 1, Scheme 2 or Scheme 3 below:

[0246] Option 1: A solution containing functional components and at least one of three components—biomass-based material, substituted biomass-based material, or surface-modified biomass-based material—is added to a coagulation bath and crushed in a crushing device. The two components are mixed and crushed simultaneously to obtain the multi-component biomass-based dispersion.

[0247] Option 2: Pour a solution containing functional components and at least one of the following three components—biomass-based material, substituted biomass-based material, or surface-modified biomass-based material—into a coagulation bath. After forming a gel, wash the solution and further crush and homogenize it with a dispersing agent to obtain the multi-component biomass-based dispersion.

[0248] Option 3: Mix at least one of the above-mentioned biomass-based dispersion, the above-mentioned substituted biomass-based dispersion, and the above-mentioned surface-modified biomass-based dispersion with a functional component to obtain the multi-component biomass-based dispersion.

[0249] According to embodiments of the present invention, the biomass-based material, the substituted biomass-based material, the surface-modified biomass-based material, the functional component, the coagulation bath, the biomass-based dispersion, the substituted biomass-based dispersion, and the surface-modified biomass-based dispersion all have the selections shown above.

[0250] [application]

[0251] The present invention also provides the application of the above-mentioned biomass-based emulsion, preferably for waterproofing paper surfaces.

[0252] According to an embodiment of the present invention, the paper surface refers to a paper surface known in the art, such as the paper surface of filter paper, kraft paper, white cardboard, corrugated paper, copy paper, cardboard, etc.

[0253] Waterproof paper

[0254] The present invention also provides a waterproof paper, which includes at least a substrate and a waterproof layer, wherein the waterproof layer is prepared by the above-mentioned biomass-based emulsion.

[0255] According to an embodiment of the present invention, the waterproof layer is disposed on at least one surface of the substrate, for example, on two surfaces.

[0256] According to an embodiment of the present invention, the substrate is selected from paper known in the art, such as filter paper, kraft paper, white cardboard, etc.

[0257] According to an embodiment of the present invention, the thickness ratio of the substrate to the waterproof layer can be any thickness ratio known in the art, and no specific limitation is made in this application, as long as the waterproof paper can be obtained.

[0258] According to an embodiment of the present invention, the waterproof paper is biodegradable.

[0259] According to an embodiment of the present invention, the water contact angle of the waterproof layer is greater than 50°, for example, 80°, 90°, 100°, 110°, 120°, or 150°.

[0260] According to an embodiment of the present invention, the Cobb value of the waterproof layer is not greater than 20 g / m².2 For example, 5g / m 2 10g / m 2 11g / m 2 12g / m 2 13g / m 2 14g / m 2 15g / m 2 16g / m 2 17g / m 2 18g / m 2 19g / m 2 .

[0261] The following detailed description, in conjunction with specific embodiments, illustrates the biomass-based materials, their preparation methods, and applications of the present invention. It should be understood that the following embodiments are merely illustrative and explanatory of the invention and should not be construed as limiting the scope of protection of the invention. All technologies implemented based on the above-described content of the present invention are covered within the scope of protection intended by the present invention.

[0262] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0263] Preparation Example 1 (Method B)

[0264] Preparation of biomass-based material dispersions:

[0265] 2.5 g of dried microcrystalline cellulose was added to 97.5 g of 1-allyl-3-methylimidazolium chloride ionic liquid ([AMIM][Cl]). After stirring at 80 °C for 2 h, a cellulose solution was obtained. The solution was poured into 500 mL of deionized water to obtain a light yellow transparent solid gel. The gel was then crushed and centrifuged, and washed repeatedly with water until no precipitate was formed when AgNO3 was added to the filtrate. The filtered gel was redispersed with water and then homogenized three times under high pressure at 450 bar to obtain a stable biomass-based material (cellulose type) dispersion.

[0266] Figure 1 Digital photographs of the micro / nanocellulose dispersion obtained in Example 1 are shown from left to right, representing the dispersion's state after standing for 0, 1, 10, 30, and 100 days. Even after 100 days of standing, the dispersion remained stable and did not separate into layers. Laser particle size analyzer measurements showed the average volume size of the micro / nano particles in the dispersion to be 13.2 μm, and scanning electron microscopy revealed a dendritic morphology.

[0267] The above dispersion was diluted with water to a solid content of 1.0 wt%.

[0268] Preparation Examples 1a-1f

[0269] The steps for preparation examples 1a-1f are the same as those for preparation example 1, except that the ionic liquid or solvent is different, as shown in Table 1-1.

[0270] Table 1-1

[0271]

[0272]

[0273] Preparation Example 1g - Preparation Example 1j

[0274] The steps for preparation examples 1g and 1j are the same as those for preparation example 1, with the differences listed in Table 1-2.

[0275] Table 1-2

[0276]

[0277] In Preparation Example 1n, the average volume size of the fibers in the dispersion was 108.7 μm, as determined by a laser particle size analyzer.

[0278] Preparation Example 2 (Method B)

[0279] Preparation of biomass-based material dispersions:

[0280] 2.5 g of dried wood pulp was added to 97.5 g of 1-allyl-3-methylimidazolium chloride ionic liquid ([AMIM][Cl]). The mixture was stirred at 80 °C for 2 h to obtain a cellulose solution. This solution was then poured into 500 mL of deionized water to obtain a yellow, transparent gel. The gel was subsequently crushed and centrifuged, and washed repeatedly with water until no precipitate was formed upon addition of AgNO3 to the filtrate. The filtered gel was then redispersed with water and subjected to high-pressure homogenization three times at 250 bar to obtain a stable biomass-based material (cellulose type) dispersion. Laser particle size analysis showed that the volume average size of the micro / nano cellulose in the dispersion was 53.1 μm.

[0281] The above dispersion was adjusted to a solid content of 1.0 wt% by adding water.

[0282] Preparation Examples 2a-2d

[0283] The steps for preparation examples 2a-2d are the same as those for preparation example 2, except that the biomass, ionic liquid or solvent is different, as shown in Table 2.

[0284] Table 2

[0285] biomass Ionic liquids solvent Preparation Example 2 Wood pulp [AMIM][Cl] Deionized water Preparation Example 2a Wood pulp [AMIM][Cl] ethanol Preparation Example 2b Wood pulp [AMIM][Cl] methanol Preparation Example 2c Wood pulp [AMIM][Cl] Isopropanol Preparation Example 2d Baka wood pulp [AMIM][Cl] Deionized water

[0286] Preparation Example 3 (Method B)

[0287] Preparation of biomass-based material dispersions:

[0288] 2.5 g of dried microcrystalline cellulose was added to 87.5 g of 1-allyl-3-methylimidazolium chloride ionic liquid ([AMIM][Cl]). After stirring at 80 °C for 2 h, 10.0 g of N,N-dimethylformamide (DMF) was added, and stirring was continued for 30 min to obtain a cellulose solution. The solution was poured into 500 mL of deionized water to obtain a light yellow transparent solid gel. The gel was then crushed and centrifuged, and washed repeatedly with water until no precipitate was formed when AgNO3 was added to the filtrate. The filtered gel was redispersed with water and then homogenized three times under high pressure at 450 bar to obtain a stable biomass-based material (cellulose type) dispersion.

[0289] Preparation Example 3a - Preparation Example 3g

[0290] The steps for preparation examples 3a-3g are the same as those for preparation example 3, except that the ionic liquid or solvent is different, as shown in Table 3-1.

[0291] Table 3-1

[0292] Ionic liquids solvent Preparation Example 3 1-Allyl-3-methylimidazolium chloride ionic liquid ([AMIM][Cl]) Deionized water Preparation Example 3a 1-Butyl-3-methylimidazolium chloride ionic liquid ([BMIM][Cl]) Deionized water Preparation Example 3b 1-Ethyl-3-methylimidazolium acetate ionic liquid ([EMIM][Ac]) Deionized water Preparation Example 3c 1-Butyl-3-methylimidazolium acetate ionic liquid ([BMIM][Ac]) Deionized water Preparation Example 3d [AMIM][Cl] ethanol Preparation Example 3e [BMIM][Cl] ethanol Preparation Example 3f [EMIM][Ac] ethanol Preparation Example 3g [BMIM][Ac] ethanol

[0293] Preparation Example 3h-3l

[0294] The steps for preparation examples 3h and 3l are the same as those for preparation example 3, with the differences listed in Table 3-2.

[0295] Table 3-2

[0296] biomass solvent Preparation Example 3h corn starch Deionized water Preparation Example 3i corn starch ethanol Preparation Example 3j Organic solvent-based lignin / 85.0g [AMIM][Cl] Deionized water Preparation Example 3k Same as preparation example 3j ethanol Preparation Example 3l Same as preparation example 3j petroleum ether

[0297] Preparation Example 4 (Method B)

[0298] Preparation of biomass-based dispersants:

[0299] 4.0 g of dried microcrystalline cellulose was added to 96.0 g of 1-allyl-3-methylimidazolium chloride ionic liquid ([AMIM][Cl]). After stirring at 80 °C for 3 h, a cellulose solution was obtained. 7.62 g of acetic anhydride was added, and the reaction was continued at 80 °C for 25 min until a transparent solution was obtained. The solution was then washed with water to allow sedimentation, followed by crushing and centrifugation. The solution was washed repeatedly with water until no precipitate was formed when AgNO3 was added to the filtrate. The solution was then homogenized three times under high pressure at 450 bar to obtain a stable substituted biomass-based material dispersion with a degree of substitution of 1.46.

[0300] Preparation Examples 4a-4d

[0301] The steps for preparation examples 4a-4d are the same as those for preparation example 4, with the differences listed in Table 4.

[0302] Table 4

[0303] Functionalized Derivatized Reagents Reaction conditions Biomass-based materials Preparation Example 4 Acetic anhydride / 0.762g Continue the reaction at 80℃ for 25 minutes. Cellulose acetate with a degree of substitution of 1.46 Preparation Example 4a Acetic anhydride / 0.762g Continue the reaction at 80℃ for 40 minutes Cellulose acetate with a degree of substitution of 1.6 Preparation Example 4b Acetic anhydride / 0.508g Continue the reaction at 80℃ for 40 minutes Cellulose acetate with a degree of substitution of 0.86 Preparation Example 4c Acetic anhydride / 0.508g Continue the reaction at 60℃ for 40 minutes Cellulose acetate with a degree of substitution of 0.65 Preparation Example 4d lactide / 1.2g Continue the reaction at 80℃ for 24 hours Cellulose-g-PLA Preparation Example 4e lactide / 0.8g Continue the reaction at 80℃ for 24 hours Cellulose-g-PLA

[0304] Preparation Example 5 (Method B)

[0305] Preparation of surface-modified biomass-based dispersions:

[0306] After preparing the micro / nano dispersion via Preparation Example 4, 3-chloro-2-hydroxypropyltrimethylammonium chloride was added to the dispersion, and the reaction was carried out at 25°C for 24 hours. The reaction solution was then centrifuged and repeatedly washed with water until no precipitate was formed upon addition of AgNO3 to the supernatant. Finally, it was redispersed in water to obtain a stable quaternized cellulose micro / nano emulsion.

[0307] Preparation Example 6 (Method B)

[0308] Preparation of surface-modified biomass-based dispersions:

[0309] After preparing the micro / nano dispersion via Preparation Example 4, sodium vinyl sulfonate was added to the dispersion and reacted at 60°C for 4 hours. The reaction solution was then centrifuged and repeatedly washed with water until no precipitate was formed upon addition of AgNO3 to the supernatant. Finally, it was redispersed in water to obtain a stable sulfonated cellulose micro / nano dispersion.

[0310] Preparation Example 7 (Method B)

[0311] Preparation of biomass-based dispersions:

[0312] 5.0 g of dried chitosan (90% degree of deacetylation) was added to 85 g of 1-butyl-3-methylimidazolium chloride ionic liquid ([BMIM][Cl]). The mixture was heated with microwave assistance for about 6 min to obtain a chitosan solution. 10.0 g of N,N-dimethylformamide (DMF) was added, and the mixture was stirred for another 30 min. The chitosan solution was then poured into 500 mL of deionized water to obtain a yellow transparent solid gel. The gel was then crushed and centrifuged, and washed repeatedly with water until no precipitate was formed when AgNO3 was added to the filtrate. The filtered gel was redispersed with water and then homogenized three times under high pressure at 450 bar to obtain a stable biomass-based material (chitosan type) dispersion.

[0313] The above dispersion was adjusted to a solid content of 1.0 wt% by adding water.

[0314] Preparation Examples 7a-7f

[0315] The steps for preparation examples 7a-7f are the same as those for preparation example 7, with the differences listed in Table 5.

[0316] Table 5

[0317]

[0318] Preparation Example 8.1 (Method A)

[0319] 4g of dried microcrystalline cellulose was added to a three-necked flask, followed by 96g of 1-allyl-3-methylimidazolium chloride ionic liquid ([AMIM][Cl]). The mixture was stirred at 80℃ for 2 hours to obtain a cellulose solution. The cellulose solution and deionized water were then added simultaneously to a conical rotor colloid mill at a volume ratio of 1:10 and ground for 30 minutes to obtain a broken gel. This gel was filtered and repeatedly washed with water until no precipitate was formed upon addition of AgNO3 to the filtrate. The filtered gel was then redispersed with water. Laser particle size analysis showed that the average volume size of the biomass-based material (micro / nano-sized cellulose) in the dispersion was 76.62 μm, and its microstructure was as follows: Figure 1 As shown, it exhibits a flocculent morphology. After drying 3–4 g of the dispersion, the yield of micronized cellulose was calculated to be 99.5%.

[0320] Preparation Examples 8.2-8.38 and Preparation Examples 8.45-8.55

[0321] The steps for preparation examples 8.2-8.38 are the same as those for preparation example 8.1, with the differences listed in Table 6.

[0322] Table 6

[0323]

[0324]

[0325]

[0326] Note: In Table 6, the unlisted coagulation baths are represented by the same deionized water as in Preparation Example 8.1; the listed baths are replaced with deionized water.

[0327] Preparation Example 9.39 (Method A)

[0328] Preparation of biomass-based dispersions:

[0329] 4g of dried wood pulp was added to 93g of 1-allyl-3-methylimidazolium chloride ionic liquid ([AMIM][Cl]) and 3g of deionized water. The mixture was stirred at 80℃ for 2 hours to obtain a cellulose solution. The cellulose solution and water were simultaneously added to a disc mill / rotor colloid mill at a volume ratio of 1:10 and ground for 30 minutes to obtain a broken gel. This gel was filtered and repeatedly washed with water until no precipitate was formed upon addition of AgNO3 to the filtrate. The filtered gel was then redispersed with water. Laser particle size analysis showed that the average volume size of the biomass-based material (micro-nano cellulose) in the dispersion was 138.35 μm, and its microstructure was as follows: Figure 12As shown, it has a fibrous structure.

[0330] Preparation Examples 9.40-9.44

[0331] The steps for preparation examples 9.40-9.44 are the same as those for preparation example 9.39, with the differences listed in Table 7.

[0332] Table 7

[0333]

[0334] Preparation Example 10.56 (Method A)

[0335] Preparation of biomass-based dispersions:

[0336] 6g of dried wood pulp was added to 91g of 1-allyl-3-methylimidazolium chloride ionic liquid ([AMIM][Cl]) and 3g of deionized water. The mixture was stirred at 90℃ for 2 hours to obtain a partially dissolved cellulose solution. The cellulose solution and ethanol were simultaneously added to a toothed rotor colloid mill at a volume ratio of 1:10 and ground for 30 minutes to obtain micro / nano-sized biomass with a fibrous morphology. This was filtered and repeatedly washed with water until no precipitation occurred upon addition of AgNO3 to the filtrate. The filtered gel was then redispersed with water to obtain a stable biomass-based material (cellulose type) dispersion. Laser particle size analysis showed that the average volume size of the fibers in the dispersion was 233.62 μm, exhibiting a fibrous morphology.

[0337] The above dispersion was adjusted to a solid content of 1.0 wt% by adding water.

[0338] Preparation Example 10.57

[0339] The steps for preparation example 10.57 are the same as those for preparation example 10.56, with the differences listed in Table 8.

[0340] Table 8

[0341]

[0342] Preparation Example 11.60 (Method A)

[0343] Preparation of biomass-based dispersions:

[0344] 15g of dried wood pulp was added to 75g of 1-allyl-3-methylimidazolium chloride ionic liquid ([AMIM][Cl]) and 10g of N,N dimethylformamide (DMF). The mixture was stirred at 80℃ for 2 hours to obtain a cellulose solution. The cellulose solution and ethanol were simultaneously added to a conical rotor colloid mill at a volume ratio of 1:10 and ground for 30 minutes to obtain a feather-like micro / nano-sized biomass. This was filtered and repeatedly washed with water until no precipitation occurred upon addition of AgNO3 to the filtrate. The filtered gel was then redispersed with water to obtain a stable biomass-based material (cellulose type) dispersion. Laser particle size analysis showed that the average volume size of the fibers in the dispersion was 141.3 μm, exhibiting a broom-like morphology.

[0345] The above dispersion was adjusted to a solid content of 1.0 wt% by adding water.

[0346] Preparation Examples 11.61-11.68

[0347] The steps for preparation examples 11.61-11.68 are the same as those for preparation example 11.60, with the differences listed in Table 9.

[0348] Table 9

[0349]

[0350] Preparation Example 12.69 (Method A)

[0351] Preparation of biomass-based dispersions:

[0352] 6g of dried cotton pulp cellulose was added to 84g of 1-allyl-3-methylimidazolium chloride ionic liquid ([AMIM][Cl]) and 10g of N,N dimethylformamide (DMF). The mixture was stirred at 80℃ for 2 hours to obtain a cellulose solution. The cellulose solution and ethanol were simultaneously added to a high-pressure homogenizer at a volume ratio of 1:10. After homogenization three times at 400 bar, a flocculent micro / nano-sized biomass was obtained. This was filtered and repeatedly washed with water until no precipitation occurred upon addition of AgNO3 to the filtrate. The filtered gel was then redispersed with water to obtain a stable biomass-based material (cellulose type) dispersion. Laser particle size analysis showed that the average volume size of the fibers in the dispersion was 43.5 μm, exhibiting a flocculent morphology.

[0353] The above dispersion was adjusted to a solid content of 1.0 wt% by adding water.

[0354] Preparation Examples 12.70-12.71

[0355] The steps for Preparation Examples 12.70-12.71 are the same as those for Preparation Example 12.69, with the differences listed in Table 10.

[0356] Table 10

[0357]

[0358] Preparation Example 13.72

[0359] Preparation of biomass-based dispersions:

[0360] 5.0 g of chitosan (90% degree of deacetylation) was weighed and dispersed in 95 g of [BMIM][Cl]. The solution was heated with microwave assistance for approximately 6 minutes until it became transparent. The chitosan solution and ethanol were then added simultaneously to a conical rotor colloid mill at a volume ratio of 1:10. After grinding for 30 minutes, a fragmented gel was obtained. This gel was filtered and repeatedly washed with water until no precipitation occurred upon addition of AgNO3 to the filtrate. The filtered gel was then redispersed with water. Laser particle size analysis showed that the average volume size of the biomass-based material (micro-nano chitosan) in the dispersion was 59.62 μm, exhibiting a flocculent morphology.

[0361] The above dispersion was adjusted to a solid content of 1.0 wt% by adding water.

[0362] Preparation Examples 13.73-13.78

[0363] The steps for preparation examples 13.73-13.78 are the same as those for preparation example 13.72, with the differences listed in Table 11.

[0364] Table 11

[0365]

[0366] Preparation Example 14.79 (Method A)

[0367] Preparation of biomass-based dispersions:

[0368] 2.5 g of dried corn starch was added to 97.5 g of 1-butyl-3-methylimidazolium chloride ionic liquid ([BMIM][Cl]), and stirred at 80 °C for 2 h to obtain a starch solution. The starch solution and ethanol were simultaneously added to a conical rotor colloid mill at a volume ratio of 1:10 and ground for 30 minutes to obtain flocculent micro / nano-sized biomass. This was filtered and repeatedly washed with water until no precipitation occurred upon addition of AgNO3 to the filtrate. The filtered gel was then redispersed with water to obtain a stable biomass-based material (starch type) dispersion. Laser particle size analysis showed that the volume average size of the biomass-based material (micro / nano-sized starch) in the dispersion was 53.27 μm.

[0369] The above dispersion was adjusted to a solid content of 1.0 wt% by adding water.

[0370] Preparation Examples 14.80-14.85

[0371] The steps for Preparation Examples 14.80-14.85 are the same as those for Preparation Example 14.79, with the differences listed in Table 12.

[0372] Table 12

[0373]

[0374] Preparation Example 15.86

[0375] Preparation of biomass-based dispersions:

[0376] Eight g of dried lignin was added to 92 g of 1-butyl-3-methylimidazolium chloride ionic liquid ([BMIM][Cl]), and stirred at 80 °C for 2 h to obtain a lignin solution. The lignin solution and ethanol were simultaneously added to a conical rotor colloid mill at a volume ratio of 1:100 and ground for 30 min to obtain flocculent micro / nano-sized biomass. This was filtered and repeatedly washed with water until no precipitation occurred upon addition of AgNO3 to the filtrate. The filtered gel was then redispersed with water to obtain a stable biomass-based material (lignin type) dispersion. Laser particle size analysis showed that the average volume size of the fibers in the dispersion was 138.35 μm.

[0377] The above dispersion was adjusted to a solid content of 1.0 wt% by adding water.

[0378] Preparation Examples 15.87-15.88

[0379] Preparation Examples 15.87-15.88 follow the same steps as Preparation Example 15.86, except that the crushing device is replaced with a disc rotor colloid mill and a toothed rotor colloid mill, respectively. The average volumetric size of the fibers in the dispersion is 98.36 μm and 177.14 μm, respectively.

[0380] The following are specific application examples of the products from the above preparation examples used in the preparation of biomass-based emulsions for waterproofing paper surfaces.

[0381] Example 1

[0382] Take the biomass-based material dispersion from Preparation Example 1 (solid content of 2 wt%, which can be processed using methods known in the art to obtain the desired concentration, the same below), add 20 g of beeswax particles with an average particle size of 100 μm to 80 g of the above biomass dispersion, and use a vortex mixer to shake the mixture evenly to obtain a biomass-based emulsion of beeswax uniformly dispersed in water. Figure 13 As shown in the middle right figure.

[0383] In this embodiment, vortex emulsification is used, which does not affect the average particle size of the beeswax particles. In the final biomass-based emulsion, the average particle size of the beeswax particles remains 100 μm. In the following embodiments, if vortex emulsification is used, it will not affect the average particle size of the raw biowax particles.

[0384] Comparative Example 1

[0385] 20g of beeswax particles with an average particle size of 100μm were added to 80g of deionized water. The mixture was shaken thoroughly using a vortex mixer, and after standing for several minutes, the suspension separated into layers. Figure 13 As shown in the middle left figure.

[0386] Example 2

[0387] Take the biomass-based material dispersion (solid content 1 wt%) from Preparation Example 2, add 4 g of palm wax to 96 g of the above biomass-based dispersion, heat to 90°C, and after the palm wax melts, stir using a high-speed disperser at 15000 rpm for 30 min to obtain a uniformly dispersed water-in-wax emulsion. Cool the emulsion to room temperature, and the molten wax re-solidifies to obtain micron-sized palm wax particles uniformly dispersed in water, with an average particle size of 103.7 μm.

[0388] Example 3

[0389] Take the biomass-based material dispersion (solid content 2 wt%) from Preparation Example 5, add 10 g of sugarcane wax to 90 g of the above biomass dispersion, heat to 90°C, and after the sugarcane wax melts, homogenize using a homogenizer for 10 min to obtain a uniformly dispersed water-in-wax emulsion. After cooling the emulsion to room temperature, the molten wax re-solidifies, obtaining micron-sized sugarcane wax particles uniformly dispersed in water with an average particle size of 81.1 μm, thus obtaining the biomass-based emulsion.

[0390] Example 4

[0391] Take the biomass-based material dispersion (solid content 2 wt%) from Preparation Example 7, add 1 g of beeswax to 99 g of the above biomass dispersion, heat to 90°C, and after the beeswax melts, stir for 10 min at 20000 rpm using a high-speed disperser to obtain a uniformly dispersed water-in-wax emulsion. Cool the emulsion to room temperature, and the molten wax re-solidifies to obtain micron-sized beeswax particles uniformly dispersed in water, with an average particle size of 58.3 μm, thus obtaining the biomass-based emulsion.

[0392] Example 5

[0393] Take the biomass-based material dispersion of Preparation Example 3j (solid content of 5wt%), add 40g of beeswax particles with an average particle size of 200μm to 60g of the above biomass dispersion, and shake the mixture evenly in a vortex cooker to obtain a biomass-based emulsion of beeswax uniformly dispersed in water.

[0394] Example 6

[0395] Take the biomass-based material dispersion (solid content 3 wt%) from Preparation Example 1n, add 2 g of wool wax to 98 g of the above biomass dispersion, heat to 60°C, and after the wool wax melts, homogenize using a homogenizer for 20 min to obtain a uniformly dispersed water-in-wax emulsion. After cooling the emulsion to room temperature, the molten wax re-solidifies, obtaining micron-sized wool wax particles uniformly dispersed in water with an average particle size of 78.6 μm, thus obtaining the biomass-based emulsion.

[0396] Example 7

[0397] Take the biomass-based material dispersion (solid content 1 wt%) from Preparation Example 8.4, add 5 g of candelilla wax to 95 g of the above biomass dispersion, heat to 80°C, and after the candelilla wax melts, stir using a high-speed disperser at 20,000 rpm for 30 min to obtain a uniformly dispersed water-in-wax emulsion. After the emulsion cools to room temperature, the molten wax re-solidifies, obtaining micron-sized candelilla wax particles uniformly dispersed in water with an average particle size of 135.6 μm, thus obtaining the biomass-based emulsion.

[0398] Example 8

[0399] Take the biomass-based material dispersion (solid content of 1 wt%) from Preparation Example 8.16, add 20 g of beeswax particles with an average particle size of 300 μm to 80 g of the above biomass dispersion, and shake the mixture evenly in a vortex cooker to obtain a biomass-based emulsion of beeswax uniformly dispersed in water.

[0400] Example 9

[0401] Take the biomass-based material dispersion (solid content 2 wt%) from Preparation Example 8.51, add 10 g of palm wax to 90 g of the above biomass dispersion, heat to 90°C, and after the palm wax melts, stir for 30 min at 20000 rpm using a high-speed disperser to obtain a uniformly dispersed water-in-wax emulsion. After cooling the emulsion to room temperature, the molten wax re-solidifies, obtaining micron-sized palm wax particles uniformly dispersed in water with an average particle size of 174.3 μm, thus obtaining the biomass-based emulsion.

[0402] Example 10

[0403] Take the biomass-based material dispersion (solid content of 1 wt%) from Preparation Example 8.56, add 10 g of beeswax particles with an average particle size of 200 μm to 90 g of the above biomass dispersion, and shake the mixture evenly in a vortex cooker to obtain a biomass-based emulsion of beeswax uniformly dispersed in water.

[0404] Example 11

[0405] Take the biomass-based material dispersion (solid content of 1 wt%) from Preparation Example 11.60, add 5 g of beeswax particles with an average particle size of 200 μm to 95 g of the above biomass dispersion, and shake the mixture evenly in a vortex cooker to obtain a biomass-based emulsion of beeswax uniformly dispersed in water.

[0406] Example 12

[0407] Take the biomass-based material dispersion (solid content of 1 wt%) from Preparation Example 12.69, add 10 g of beeswax particles with an average particle size of 100 μm to 90 g of the above biomass dispersion, and shake the mixture evenly in a vortex cooker to obtain a biomass-based emulsion of beeswax uniformly dispersed in water.

[0408] Example 13

[0409] Take the biomass-based material dispersion (solid content of 5 wt%) from Preparation Example 13.72, add 40 g of beeswax particles with an average particle size of 100 μm to 60 g of the above biomass dispersion, and shake the mixture evenly in a vortex cooker to obtain a biomass-based emulsion of beeswax uniformly dispersed in water.

[0410] Table A lists the components and amounts of the emulsions used in Examples 1-13.

[0411]

[0412] Test Example 1

[0413] The bio-wax emulsions prepared in Examples 1-13 above were coated onto white cardboard, and after drying, white cardboard with different surface waterproofing treatments was obtained.

[0414] The water contact angle and Cobb value of untreated white cardboard and white cardboard with the above-mentioned surface waterproofing treatment were tested (refer to GB / T1540-2002 "Determination of water absorption of paper and paperboard (Cobb method)"). The test results are shown in Table B. Figure 14 This reflects the situation of adding gentian violet aqueous solution to untreated white cardboard and white cardboard treated with the bio-wax emulsion of Example 1.

[0415] Table B Test Results

[0416] Water contact angle (°) <![CDATA[Cobb value (g / m 2 ) <!-- 28 -->]]> Untreated white cardboard ～40 26.0 Example 1 120 12.9 Example 2 115 15.3 Example 3 93 14.8 Example 4 108 12.0 Example 5 122 12.7 Example 6 131 13.3 Example 7 105 15.5 Example 8 119 13.6 Example 9 114 11.7 Example 10 116 14.4 Example 11 120 13.1 Example 12 119 12.8 Example 13 118 12.5

[0417] The specific embodiments of the present invention have been described above by way of example. However, the scope of protection of the present invention is not limited to the above exemplary embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A biomass-based emulsion, characterized in that, The biomass-based emulsion comprises biomass-based materials and biowax; the biomass-based materials comprise micron-scale structures and nano-scale structures distributed on the micron-scale structures.

2. The biomass-based emulsion according to claim 1, characterized in that, The biomass-based material is prepared using either method A or method B as follows: Method A includes the following steps: Biomass is dissolved in a solvent to form a biomass solution; The biomass solution and coagulation bath are added to a crushing device, and the two are crushed while being mixed; the biomass-based material is then prepared. Method B includes the following steps: pouring a biomass solution into a coagulation bath to form a biomass gel; and performing micro-nano processing on the biomass gel through mechanical crushing to obtain the biomass-based material.

3. The biomass-based emulsion according to claim 1 or 2, characterized in that, The micron-level structure includes at least one of micron-sheets, micron-fibers, and micron-level structures. Preferably, the micron-scale structure is fibrous or membrane-like. Preferably, the nanoscale structure is distributed on the surface and / or edges of the micrometer-scale structure. Preferably, the nanoscale structure is densely distributed on the surface and / or edges of the micrometer-scale structure. Preferably, the nanoscale structure is distributed on the micrometer-scale structure and thus forms a flocculent structure. Preferably, the nanoscale structure is distributed on the micrometer-scale structure, thereby forming an overall structure similar to a porous sponge. Preferably, the nanoscale structure and the micrometer-scale structure together form a feather-like structure. Preferably, the nanoscale structure is in the form of a villous, tentacle-like, whisker-like, or other irregular structure. Preferably, the biomass-based material has a fibrous, sheet-like, feather-like, branch-like, flocculent, or porous sponge-like structure. Preferably, in the biomass-based emulsion, the mass ratio of the biomass-based material to the biowax is (0.01-10):(0.1-50). Preferably, the biowax is selected from at least one of animal wax and plant wax.

4. A biomass-based emulsion, characterized in that, The biomass-based emulsion comprises a biomass-based dispersion and a biowax. The dispersion includes the biomass-based material and a dispersing agent as described in any one of claims 1-3. The biomass-based material and the biowax are distributed in the dispersing agent, which is a solvent system capable of continuously dispersing the biomass-based material and the biowax. Preferably, in the biomass-based emulsion, the mass ratio of the biomass-based material to the biowax is (0.01-10):(0.1-50). Preferably, the biowax is selected from at least one of animal wax and plant wax.

5. A biomass-based emulsion, characterized in that, The biomass-based emulsion includes biowax and surface-modified biomass-based material or surface-modified biomass-based dispersion; the surface-modified biomass-based dispersion includes surface-modified biomass-based material and dispersing agent, wherein the surface-modified biomass-based material and biowax are dispersed in the dispersing agent; The dispersing agent is a solvent system capable of continuously dispersing the surface-modified biomass-based material and the biowax; the surface-modified biomass-based material is a surface-modified version of the biomass-based material according to any one of claims 1-3; or a material prepared by the preparation method of the biomass-based material according to claim 2, except that the raw biomass is replaced with surface-modified biomass. Preferably, in the biomass-based emulsion, the mass ratio of the surface-modified biomass-based material to the biowax is (0.01-10):(0.1-50). Preferably, the biowax is selected from at least one of animal wax and plant wax.

6. A biomass-based emulsion, characterized in that, The biomass-based emulsion comprises biowax and a substituted biomass-based material or a substituted biomass-based dispersion; the substituted biomass dispersion comprises a substituted biomass-based material and a dispersing agent, wherein the substituted biomass-based material and biowax are dispersed in the dispersing agent; the dispersing agent is a solvent system capable of continuously dispersing the substituted biomass-based material and biowax; the biomass-based material in the substituted biomass-based dispersion is the biomass-based material according to any one of claims 1-3; or a material prepared by the preparation method of the biomass-based material according to claim 2, except that the raw biomass is replaced with surface-modified biomass. Preferably, in the biomass-based emulsion, the mass ratio of the substituted biomass-based material to the biowax is (0.01-10):(0.1-50). Preferably, the biowax is selected from at least one of animal wax and plant wax.

7. A biomass-based emulsion, characterized in that, The biomass-based emulsion comprises biowax and a multi-component biomass-based dispersion, wherein the continuous phase of the biomass-based emulsion is a dispersing agent, and the dispersed phase of the biomass-based emulsion contains biowax and functional components, and also contains at least one of the following components 1) to 3): 1) The biomass-based material according to any one of claims 1-3; 2) The alternative biomass-based material as described in claim 6; 3) The surface-modified biomass-based material as described in claim 5. Preferably, in the biomass-based emulsion, the mass ratio of at least one of components 1) to 3) to biowax is (0.01 to 10): (0.1 to 50). Preferably, the biowax is selected from at least one of animal wax and plant wax.

8. The biomass-based emulsion according to claim 7, characterized in that, The functional components are selected from one or more of the following substances: nanocellulose, carbon nanotubes, graphene, fullerene, carbon black, silver nanowires, quantum dots, carbon dots, nanoFe3O4, and drugs.

9. The biomass-based emulsion according to any one of claim 4, 5, 6, or 7, characterized in that, The dispersing agent is selected from at least one of water, alcohol, alcohol-water mixture, HCl aqueous solution, NaOH aqueous solution, and inorganic salt aqueous solution.

10. The application of the biomass-based emulsion according to any one of claims 1-9 in the waterproofing treatment of paper surfaces.

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